Regio- and Stereoselective Homologation of 1,2-Bis(Boronic Esters): Stereocontrolled Synthesis of 1,3-Diols and Sch 725674.

ABSTRACT: 1,2-Bis(boronic esters), derived from the enantioselective diboration of terminal alkenes, can be selectively homologated at the primary boronic ester by using enantioenriched primary/secondary lithiated carbamates or benzoates to give 1,3-bis(boronic esters), which can be subsequently oxidized to the corresponding secondary-secondary and secondary-tertiary 1,3-diols with full stereocontrol. The transformation was applied to a concise total synthesis of the 14-membered macrolactone, Sch 725674. The nine-step synthetic route also features a novel desymmetrizing enantioselective diboration of a divinyl carbinol derivative and high-yielding late-stage cross-metathesis and Yamaguchi macrolactonization reactions.

SUBMITTER: Fawcett A 

PROVIDER: S-EPMC5129522 | biostudies-literature | 2016 Nov

REPOSITORIES: biostudies-literature